CN103143252A - Additive capable of simultaneous desulphurization and demercuration and preparation method thereof - Google Patents
Additive capable of simultaneous desulphurization and demercuration and preparation method thereof Download PDFInfo
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- CN103143252A CN103143252A CN2013100561105A CN201310056110A CN103143252A CN 103143252 A CN103143252 A CN 103143252A CN 2013100561105 A CN2013100561105 A CN 2013100561105A CN 201310056110 A CN201310056110 A CN 201310056110A CN 103143252 A CN103143252 A CN 103143252A
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- additive
- demercuration
- desulfuration demercuration
- adipic acid
- desulfuration
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Abstract
The invention discloses an additive capable of simultaneous desulphurization and demercuration. The additive comprises sodium benzoate, ferric sulfate, adipic acid and ortho-phthalaldehyde. The invention further discloses a preparation method for the additive capable of simultaneous desulphurization and demercuration. The additive can realize simultaneous desulphurization and demercuration, has high desulphurization and demercuration efficiency and has the advantages of improvement of activity of limestone, capacity of preventing fouling and blocking of a WFGD system and reduction of system energy loss.
Description
Technical field
The present invention relates to a kind of desulfuration demercuration additive, be specifically related to a kind of while desulfuration demercuration additive.The invention still further relates to the preparation method of this additive.
Background technology
It is the major issue that environmental protection for electric power faces that the flue gas pollutant of coal-burning power plant is controlled always, and at present, the application of the equipment such as flue gas desulfurization and denitrification and deduster can make flue gas substantially satisfy existing pollutant emission standard.Desulfuration efficiency is high, applicability is wide because Wet Flue Gas Desulfurization Technique has, and China all adopts the coal-burning power plant more than 90% Gypsum Wet (WFGD) to carry out flue gas desulfurization.Mercury has serious physiology toxicity, " fossil-fuel power plant atmospheric pollutant emission standard " (GB 13223-2011) clear of China's issue in 2011, and the emission limit of mercury and mercuric compounds is 0.03mg/m
3Along with the continuous attention to the power station mercury pollution, FGD also attracts wide attention the impact of mercury pollution emission performance, if when not affecting the normal desulfurization operation of WFGD, utilizing existing wet desulfurization system can effectively control the discharging of mercury, will be the following pollutant control method of good economic benefits that is hopeful most and has.
It is gaseous state Hg that there are three kinds of forms in mercury in coal-fired flue-gas usually
0, divalent state Hg
2+With the solid granulates attachment.Particle mercury is easily captured and is removed by dust arrester, and gaseous mercury is because volatility is high, and is water-soluble low, be difficult to be removed by existing dust arrester, and oxidation state Hg
2+Soluble in water, be easy to be removed by WFGD.Therefore, the height of WFGD system demercuration rate depends on Hg in flue gas
2+Content, and actual motion test is found, the Hg of power-plant flue gas 80% is with Hg
0Form exist, although the WFGD system is to Hg
2+Higher clearance being arranged, the clearance of full mercury is still allowed of no optimist, therefore, is to improve flue gas demercuration efficient, and present research concentrates on the Hg in flue gas
0Be oxidized to as far as possible Hg
2+Removed by wet desulphurization device again.
Process the general solid absorbent that adopts for the desulfuration demercuration of flue gas, be respectively mercury removal agent and desulfurizing agent.Demercuration adsorbent commonly used has active carbon, flying dust, calcium base class adsorbent etc.And the research of fume desulfurizing agent is comparatively ripe, and main desulfurizing agent has calcium-based desulfurizing agent, sodium base desulfurizer, amido desulfurizing agent, Mg-base desulfurizing agent, metal oxide desulfurizer and citric acid desulfurizing agent and adsorption desulfurizing agent etc.Wet process of FGD generally adopts calcium-based desulfurizing agent such as lime stone (CaCO
3).At present, during power-plant flue gas is processed, mercury removal agent and desulfurizing agent are all independent uses, and the use of desulfurizing agent can reach higher desulfuration efficiency, and the application of especially current sulfur-removing additives more can effectively improve system's limestone activity, improve the problem that scaling stops up, desulfurization degree is up to more than 99%, but fails to significantly improve flue gas demercuration efficient, and the independent use of mercury removal agent can effectively improve flue gas demercuration efficient, but because the high operating cost that causes of the price of adsorbent own is high, can't be applied.Therefore, present mercury removal agent and desulfurizing agent all can not solve the obstruction of WFGD scaling and the not high problem of demercuration efficient well.
Summary of the invention
First purpose of the present invention is to provide a kind of while desulfuration demercuration additive, this additive is desulfuration demercuration simultaneously both, has higher desulfuration demercuration efficient, also has the raising limestone activity, prevent WFGD scaling and obstruction, reduce the advantage of system capacity loss.
Second purpose of the present invention is to provide the preparation method of above-mentioned additive.
The 3rd purpose of the present invention is the application of above-mentioned additive.
The objective of the invention is to be achieved through the following technical solutions: a kind of while desulfuration demercuration additive is comprised of Sodium Benzoate, ferric sulfate, adipic acid and OPA.
As an embodiment of the invention, described each weight percentages of components of desulfuration demercuration additive is:
Sodium Benzoate 35%-50%, ferric sulfate 20%-25%, adipic acid 22%-35%, OPA 8%-15%.
In the present invention, Sodium Benzoate can accelerate the dissolving of lime stone in wet desulfurization system as cosolvent, prevents that in the WFGD system, fouling is stopped up; Adipic acid is organic acid, thereby can promote the mass transfer fast reaction speed between wet desulfurization system air film and liquid film; Ferric sulfate is conducive to Hg as oxidant
0To Hg
2+Conversion; OPA is conducive to and Hg as organic aldehyde material
2+Form chelate, suppress Hg
2+Reduction.Four kinds of component performance effects are separately complemented each other again, reach and improve desulfuration demercuration efficient, and improve limestone activity, prevent WFGD scaling and obstruction, reduce the system capacity loss.
Second purpose of the present invention is achieved through the following technical solutions: a kind of preparation method of while desulfuration demercuration additive, Sodium Benzoate, ferric sulfate, adipic acid and OPA are mixed by proportioning, adding water mixes, heating water bath also constantly is stirred to each components dissolved, make composite solution, then dry 12～24h at 100 ~ 105 ℃ of temperature, be cooled to room temperature, makes the desulfuration demercuration additive.
The application of the above-mentioned desulfuration demercuration additive of the present invention in the desulfurization of coal-fired plant flue gas demercuration.
The method that adds of desulfuration demercuration additive of the present invention is: can add in the optional position of slurries closed circuit, propose different schemes according to power plant's time ruuning situation.If add in serum producing system, its using method is, requirement according to WFGD system desulphurization plant is made lime stone slurry with desulfurizing agent (lime stone) and water mix and blend, then add desulfuration demercuration additive of the present invention in lime stone slurry, its addition is 3.5 ‰ of lime stone weight, then stir and the desulfuration demercuration additive is fully mixed with lime stone slurry contact, mixing time is 24-36 hour, whipping temp is 50-60 ℃, after mixing fully, slurries is delivered to flue gas desulfurization device.In setting up desulphurization system absorption tower slurries during the background concentration of desulfuration demercuration additive, can use agitator that desulfuration demercuration additive stirring and dissolving is directly squeezed into the absorption tower by the ground pump after evenly.
Compared with prior art, the present invention has following beneficial effect:
1. desulfuration demercuration additive of the present invention can significantly improve the desulfuration demercuration efficient of wet desulfurizing process, and it can be effectively with the Hg in flue gas
0Be oxidized to Hg
2+Thereby, mercury is converted into stable low toxicity compounds, be dissolved in the slurries of absorption tower, form the insoluble matter precipitation with sulphion etc., through Separation of Solid and Liquid, mercury is thoroughly removed, solved its potential secondary pollution problem, the pollution of minimizing to environment has good economic and social benefit.Simultaneously, add chelating agent in sulfur and mercury removing agent and can effectively suppress Hg
2+Reduction discharge, thereby strengthen the demercuration ability of wet desulfurization system.
2. the present invention not only has the catalytic reaction effect, has also improved limestone activity, prevents the fouling of WFGD system equipment and obstruction, effectively improves the utilization rate of wet desulfurization system desulfurizing agent, and reduces the system capacity loss, to coal-fired flue-gas SO
2Has good effect with the improvement of Hg.
3. desulfuration demercuration additive of the present invention can utilize the existing wet desulfurization system removal of mercury, reaches the effect of pollutant control preferably with lower operation cost of investment, has a extensive future.
The specific embodiment
Embodiment 1
Sodium Benzoate, ferric sulfate, adipic acid and OPA are mixed according to the constant weight proportioning, wherein, Sodium Benzoate 40wt%, ferric sulfate 20wt%, adipic acid 30wt%, OPA 10wt%.Add water and mix, in 60 ℃ of lower heating water baths and constantly stirring, each component is fully dissolved, make composite solution, 105 ℃ of dry 24h are cooled to room temperature, make the desulfuration demercuration additive.
Embodiment 2
Sodium Benzoate, ferric sulfate, adipic acid and OPA are mixed according to the constant weight proportioning, wherein, Sodium Benzoate 35wt%, ferric sulfate 22wt%, adipic acid 32wt%, OPA 11wt%.Add water and mix, in 60 ℃ of lower heating water baths and constantly stirring, each component is fully dissolved, make composite solution, 105 ℃ of dry 12h are cooled to room temperature, make the desulfuration demercuration additive.
Embodiment 3
Sodium Benzoate, ferric sulfate, adipic acid and OPA are mixed according to the constant weight proportioning, wherein, Sodium Benzoate 42wt%, ferric sulfate 22wt%, adipic acid 28wt%, OPA 8wt%.Add water and mix, in 60 ℃ of lower heating water baths and constantly stirring, each component is fully dissolved, make composite solution, 105 ℃ of dry 20h are cooled to room temperature, make the desulfuration demercuration additive.
Embodiment 4
Sodium Benzoate, ferric sulfate, adipic acid and OPA are mixed Sodium Benzoate 44wt% wherein, ferric sulfate 20wt%, adipic acid 26wt%, OPA 10wt% according to the constant weight proportioning.Add water and mix, in 60 ℃ of lower heating water baths and constantly stirring, each component is fully dissolved, make composite solution, 105 ℃ of dry 18h are cooled to room temperature, make the desulfuration demercuration additive.
Embodiment 5
Sodium Benzoate, ferric sulfate, adipic acid and OPA are mixed according to the constant weight proportioning, wherein, Sodium Benzoate 46wt%, ferric sulfate 22wt%, adipic acid 24wt%, OPA 8wt%.Add water and mix, in 60 ℃ of lower heating water baths and constantly stirring, each component is fully dissolved, make composite solution, 105 ℃ of dry 23h are cooled to room temperature, make the desulfuration demercuration additive.
Embodiment 6
Sodium Benzoate, ferric sulfate, adipic acid and OPA are mixed according to the constant weight proportioning, wherein, Sodium Benzoate 42wt%, ferric sulfate 24wt%, adipic acid 25wt%, OPA 9wt%.Add water and mix, in 60 ℃ of lower heating water baths and constantly stirring, each component is fully dissolved, make composite solution, 105 ℃ of dry 15h are cooled to room temperature, make the desulfuration demercuration additive.
Experimental example:
The desulfuration demercuration additive that makes with embodiment 1 to 6 adds in lime stone slurry, and addition is 3.5 ‰ of lime stone weight, and lime stone slurry density is 1100kg/m
3~ 1200kg/m
3, pH is 5.5 ~ 5.8, and the desulfuration demercuration additive added rear mix and blend 24 ~ 36 hours, and whipping temp is 50 ~ 60 ℃, after mixing fully, slurries is delivered to desulfuration absorbing tower.The simulated flue gas constituent that passes in the absorption tower is O
2Be 3%, CO
2Be 12%, Hg
0Be 0.3mg/m
3, SO
2Be 2000ppm, HCl is 5ppm, and all the other are N
2, temperature is 60 ℃, controls gas flow and be under 1L/min the desulfuration demercuration additive to mercury and sulfur dioxide (SO
2) removal efficient.The results are shown in Table 1.
The present invention can summarize with other the concrete form without prejudice to spirit of the present invention or principal character.Above-mentioned embodiment of the present invention all can only be thought explanation of the present invention rather than restriction, therefore every foundation essence technology of the present invention to any trickle modification, equivalent variations and modification that above embodiment does, all belongs in the scope of technical solution of the present invention.
Claims (5)
1. a while desulfuration demercuration additive, is characterized in that, is comprised of Sodium Benzoate, ferric sulfate, adipic acid and OPA.
2. while desulfuration demercuration additive according to claim 1, is characterized in that, the percentage by weight of the component of described additive is:
Sodium Benzoate 35%-50%, ferric sulfate 20%-25%, adipic acid 22%-35%, OPA 8%-15%.
3. the preparation method of the desulfuration demercuration additive of described while of claim 1 or 2, it is characterized in that, Sodium Benzoate, ferric sulfate, adipic acid and OPA are mixed by proportioning, adding water mixes, heating water bath also constantly is stirred to each components dissolved, makes composite solution, then dry 12～24h at 100 ~ 105 ℃ of temperature, be cooled to room temperature, make the desulfuration demercuration additive.
4. the application of desulfuration demercuration additive of described while of claim 1 or 2 in the desulfurization of coal-fired plant flue gas demercuration.
5. application according to claim 4, is characterized in that, the addition of described desulfuration demercuration additive is 3.5 ‰ of lime stone weight.
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| CN103143252B CN103143252B (en) | 2015-06-10 |
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Cited By (3)
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|---|---|---|---|---|
| CN103341310A (en) * | 2013-07-03 | 2013-10-09 | 上海交通大学 | Method for recycling gas-state zero-valence mercury and sulfur dioxide from non-ferrous metal metallurgy smoke gas |
| CN106000275A (en) * | 2016-06-20 | 2016-10-12 | 广东电网有限责任公司电力科学研究院 | Adsorbent and preparation method and application thereof |
| CN112058071A (en) * | 2020-07-24 | 2020-12-11 | 中国恩菲工程技术有限公司 | Demercuration slurry and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112058071A (en) * | 2020-07-24 | 2020-12-11 | 中国恩菲工程技术有限公司 | Demercuration slurry and preparation method thereof |
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| CN103143252B (en) | 2015-06-10 |
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Effective date of registration: 20171116 Address after: 510655, No. fifth, No. 146-150, Whampoa Avenue, Tianhe District, Guangdong, Guangzhou Patentee after: Guangdong Electric Power Research Institute of energy technology limited liability company Address before: 510080 Dongfeng East Road, Dongfeng, Guangdong, Guangzhou, Zhejiang Province, No. 8 Patentee before: ELECTRIC POWER RESEARCH INSTITUTE, GUANGDONG POWER GRID CO., LTD. |
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Address after: Room 501-503, annex building, Huaye building, No.1-3 Chuimao new street, Xihua Road, Yuexiu District, Guangzhou City, Guangdong Province 510000 Patentee after: China Southern Power Grid Power Technology Co.,Ltd. Address before: 510655 5th floor, no.146-150, Huangpu Avenue Middle Road, Tianhe District, Guangzhou City, Guangdong Province Patentee before: GUANGDONG ELECTRIC POWER SCIENCE RESEARCH INSTITUTE ENERGY TECHNOLOGY Co.,Ltd. |